Au/CeO<sub>2</sub>催化剂上CO<sub>2</sub>选择加氢为CO反应及其中间物种研究

引用本文: 朱晓兵, 曲新, 李小松, 刘景林, 刘剑豪, 朱斌, 石川. Au/CeO₂催化剂上CO₂选择加氢为CO反应及其中间物种研究[J]. 催化学报, 2016, 37(12): 2053-2058. doi: 10.1016/S1872-2067(16)62538-X shu

Citation: Xiaobing Zhu, Xin Qu, Xiaosong Li, Jinglin Liu, Jianhao Liu, Bin Zhu, Chuan Shi. Selective reduction of carbon dioxide to carbon monoxide over Au/CeO₂ catalyst and identification of reaction intermediate[J]. Chinese Journal of Catalysis, 2016, 37(12): 2053-2058. doi: 10.1016/S1872-2067(16)62538-X shu

Au/CeO₂催化剂上CO₂选择加氢为CO反应及其中间物种研究

大连理工大学氢能与液体燃料研究中心;等离子体物理化学实验室, 辽宁大连 116024
基金项目:
国家自然科学基金（11475041，11175036，21373037），中央高校基本科研业务费（DUT16QY49）.

摘要: CO₂的化学转化具有环境及科学双重研究意义.CO₂具有很高的化学稳定性，加氢还原是一种有效的转化途径.其中将CO₂选择性还原为CO，即逆水汽变换（RWGS）反应（CO₂+H₂→ CO+H₂O），具有重要的理论意义和应用价值：（1）CO作为合成气的重要原料，可以通过F-T合成生产更有价值的液体燃料；（2）H₂可通过可再生能源电解水制取，实现了全过程的零排放碳循环利用.
从热力学角度分析，RWGS反应是一个吸热反应，高温有利于平衡转化率的提高.从动力学角度，一个对正反应有活性的催化剂可同时催化逆反应进行.可还原性载体负载贵金属催化剂，如Pt/CeO₂，Au/FeO_x，Au/CeO₂等，具有很好的低温WGS催化活性，但它们在RWGS反应上的研究较少.我们制备了CeO₂负载纳米Au催化剂（HRTEM表征结果表明金高度分散于CeO₂载体表面，粒径为4-5 nm），其在常压CO₂加氢还原为CO反应中表现出优异的低温活性，分别在450℃，CO₂/H₂=1，WHSV=12000 mL/（h·g），及400℃，H₂/CO₂=1，WHSV=6000 mL/（h·g）条件下，CO₂转化率接近平衡转化率，且CO的选择性为100%.随着H₂/CO₂比例增加，CO₂转化率明显提高，且维持H₂/CO₂为1的化学计量比反应.通过原位漫反射红外光谱与质谱相结合的技术，研究了Au/CeO₂催化剂上的RWGS反应路径：Au/CeO₂催化剂表面形成了甲酸盐中间物种，它的消耗伴随着CO和H₂O产物的生成.说明Au/CeO₂催化剂遵循中间体机理，这应该是其具有优异低温RWGS反应性能的微观机制.

关键词:

English

Selective reduction of carbon dioxide to carbon monoxide over Au/CeO₂ catalyst and identification of reaction intermediate

Center for Hydrogen Energy and Liquid Fuels;Laboratory of Plasma Physical Chemistry, Dalian University of Technology, Dalian 116024, Liaoning, China
Received Date: 23 August 2016
Revised Date: 29 September 2016
Fund Project:
This work was supported by the National Natural Science Foundation of China (11475041, 11175036, 21373037), and the Fundamental Research Funds for the Central Universities (DUT16QY49).

Abstract: CO₂ selective reduction to CO with H₂ over a CeO₂-supported nano-Au catalyst at atmospheric pressure was investigated. A high CO₂ conversion, approaching the thermodynamic equilibrium value, and nearly 100% CO selectivity were obtained. The surface formate intermediates generated during the reverse water-gas shift reaction at 400℃ were identified using in situ diffuse-reflectance infrared Fourier-transform spectroscopy. The formate consumption to give CO and H₂O, determined using mass spectrometry, indicated that the reaction proceeded via an associative formate mechanism; this contributes to the high Au/CeO₂ catalytic activity at low temperatures.

Key words:

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Au/CeO₂催化剂上CO₂选择加氢为CO反应及其中间物种研究

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Selective reduction of carbon dioxide to carbon monoxide over Au/CeO₂ catalyst and identification of reaction intermediate

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Selective reduction of carbon dioxide to carbon monoxide over Au/CeO2 catalyst and identification of reaction intermediate

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